Spinning artificial threads



Patented Feb. 13, 1940 UNITED STATES PATENT OFFICE SPINNING ARTIFICIAL THREADS No Drawing.

rial No. 118,916. 1931 15 Claims.

Our present invention relates to spinning of artificial threads and more particularly to'spinning of artificial threads from resins. It is a continuation in part of our application Ser. No.

One of its objects is the process of spinning artificial threads from resins which have an increased tensile strength in the dry, as well as in the wet state.

10 Another object are the artificial threads of resins having an increased tensile strength. Further objects will be seen from the detailed specification following hereafter.

, The proposal of spinning artificial threads from resins has frequently been made. The mechanical properties of the threads thus obtained, however, are far from being satisfactory. At best their tensile strength amounts only to 50 to 90 grams per 100 deniers and their extensibility is at most 10 per cent, so that in no way they fulfil the requirements of the textile industry.

The present invention permits the manufacture from resins of threads which have a high tenacity and extensibility and in respect to their mechanical properties are not only equal, but even superior to the usual artificial silks, such as viscose silk or cuprammonium silk. For example, there are obtained threads having a tensile strength from about 1.5 to 2.4 grams per 80 denier. The process of this manufacture consists in spinning a solution of the resin in a precipitating bath of considerable length according to the wet spinning process so as to produce a. thread which is strongly swollen and is there- 39 fore plastic and elastic and stretching the thread after it has left the spinning bath in one or more stages, for instance between rollers, rotating at peripheral speeds which increase from roller to roller until it has been extended to a multiple 10 of the length which it had originally, when ejected through the nozzle into the spinning bath. The stretched threads may be finished by washing and drying the same.

The spinning bath must be long enough to '5 allow of a thorough coagulation of the filament. While the length of the bath varies considerably with the diiferent solvents for the artificial resin and with the composition of the spinning bath it may be said that it must not be considerably smaller than one meter.

The stretching operation may be efiected during the spinning process by means of driven rollers. Thus, for instance the devices described in U. S. Patents Nos. 1,401,943, 1,450,131, German Patent No. 527,085 or in the copending applica- Application January 2, 1937, Se-

In Germany October 19,

tion Ser. No. 416,985 filed December 27, 1929, by Pfannenstiel et al., now Patent No. 1,933,999, for spinnig cellulose threads, have proved advantageous. It is also possible to influence the physical properties of the threads by allowing the 5 stretched thread to shrink between the last stretching roller and the collecting device by diminishing the draught of the latter, for instance as described in the co-pending application Ser. No. 608,802, filed May 2, 1932, by Pfannenstiel et al., now PatentNo. 2,078,339.

It is not absolutely necessary that the threads should be stretched by means of stretching rollers; any stretching devices known for stretching cellulose threads are suitable for the purpose. Thus, the stretching operation may be carried out by means of staggered, non-driven rollers or rods or fork prongs which exert a braking action on the thread after it leaves the nozzle so that it can be drawn out to a fine capillary titer. By

stretching. the threads in the manner described, even the strength of threads made of resins may be considerably increased.

As starting material for the process according to this invention those resins are suited which according to the present state of science consist of molecules having very long chains. Resins of the kind described are, for instance, the polymerization products and mixed polymerizates of vinyl compounds as they are produced from a monomeride of the general formula CH2==CHR by conversion into the polymeride (CH2-CI'IR)n, B being Cl, 'CN, COOCHs, CsHs, NH2, OH, O.CO.CH3, O.CO.CH2C1, COCH: or the like. Other suitable substances are the mixed polymerization products of these compounds with a-dichlorethylene (CH2=CC12) or maleic anhydride, as well as the esters of aliphatic or aromatic dicarboxylic acids with polyhydric, particularly dihydric alcohols. The use of mixtures of several resins may also yield good results. If desired the spinning solution may contain an addition of a softening agent, a textile oil or an agent having a protective action against the action of oxygen or light.

The following examples serve to illustrate the invention: 1

Example 1.--The surprising technical elfect obtained by the invention is illustrated by the result obtained with highly viscous polyvinyl chlorides. Such a polyvinylchloride is obtainable by polymerizing vinylchloride in an autoclave in the presence of benzoylperoxide and acetic acid anhydride at a temperature of about 35-40 C. until the product is nearly insoluble in the usual sol- I vents, for instance, benzene or acetone, and only strongly swellable in methylene chloride or tetrachlorethane. parts by weight of this product are dissolved in 85 parts by weight of cyclohexanone and stirred for along time at ordinary temperature. The viscosity of the spinning solution was after this stirring 2400 seconds (determined by the time taken by a steel-ball of a diameter of 3.17 mm. and a weight of 0.133 gram to fall on a distance of cm. through the viscous solution at a temperature of 20 C.) The solution is then pressed after the usual deaeration and filtration through a nozzle having perforations of 0.09 mm. diameter each into a precipitating bath comprising acetic acid 01 30 per cent strength. The speed of injection amounts to 12.3 meters per minute. The coagulated thread is stretched after an immersion length 01' 2.5 meters between drawing rollers in three successive stages.

The peripheral speeds of the rollers are gradated as follows:

Meters per minute (a) Drawing roller after the precipitating bath 8.6 (1)) First drawing roller 13.8 (0) Second drawing roller 19.2 (d) Winding up roller 26.4

The artificial silk thus spun is dried after twisting and reeling at normal temperature. The tensile strength amounts at a total titer of 160 deniers and a single titer of 4 deniers to 170 grams per 100 deniers with 30% extensibility. The tensile strength in the wet state surprisingly is higher than the tensile strength in the dry state and amounts to 190 grams per 100 deniers, while the extensibility is 30%.

Example 2.The same solution as in Example 1 is heated for 1 hour at to C. and spun after the cooling to room temperature. The threads spun from the same nozzle as described in Example 1 at a speed on injection of 13.4 meters are guided through a precipitating bath of 1 meter length containing acetic acid of 30% by volume and extended after leaving the bath by drawing rollers having the following peripheral speeds:

Meters per minute (a) Drawing roller after the precipitating bath- 8.6 (b) First drawing roller 20. (0) Second drawing roller 24.0 (d) Winding up roller 35.0

3.6 cc. into an aqueous solution of sodium perchlorate of 50%. The immersion length is four to five meters. The coagulated thread is then extended by means of drawing rollers having the following peripheral speeds.

Meters per minute (a) Drawing roller after the precipitating bath 8.8 (b) First drawing roller 13.8 (1;) Second drawing roller 16.2 (d) Winding up roller 22.3

With a titer of 220 deniers the extensibility of the thread amounts to 1.25 grams. per denier at an elongation of 83% 4 Example 4.A 22.5% solution of after-chlorinated polyvinylchloride, which is described in U. S. 6

Patent No. 1,982,765, having a chlorine content of 63 to 64% in cyclohexanol is spun into methanol through a spinning nozzle having 40 bores of 0.08 mm. diameter each at a speed of injection of 14.2 meters per minute, while the spinning pump supplies 2.85 cc. After an immersion length 01' 4 to 5 meters the thread is guided over a stretching device consisting of three glass rods each out of line with the other two by which it is braked to such an extent that the velocity oi the thread between the spinning nozzle and the stretching device is reduced to 16 to 17 meters per minute, that is to say approximately to the speed of injection. From the fork the thread is immediately wound on a spinning spool having a peripheral speed of 45.6 meters. There are obtained threads of a titer of deniers having a breaking load between 150 and grams with an extensibility of 14 to 18%, according to the immersion length withinthe range Just mentioned.

Example 5.A 30% solution of after-chlorinated polyvinylchloride, which is described in U. 8. Patent No. 1,982,765, in acetone is spun at a speed of injection of nine meters per minute while supplying 2.7 cc. through a spinning nozzle having 60 bores of 0.08 mm. diameter each into water as a precipitating bath. The immersion length is 1.8 meters. The extension by means of a stretching device consisting of three rods each out of line with the other two brakes to such an extent that the spinning speed between the nozzle and the rods is diminished similarly as described in Example 4. The threads are wound on a spinning spool rotating at 48 meters per minute. There is obtained a silk thread of a titer of 150 deniers with a breaking load of 172 grams, while the extensibility amounts to 17%.

Example 6.A 22.5% solution in acetone of the mixed polymerization product of 80 parts of polyvinylchloride and 20 parts of acrylic acid ester is spun at a speed of injection of 18 meters per minute while supplying 3.6 cc. through a spinning nozzle having 40 bores of 0.08 mm. diameter each into water as described in Example 5. The length of the precipitating bath is 2 meters, the stretching device is the same as described in the preceding example. There is obtained a silk of a titer of 150 deniers with a tensile strength of 200 grams and 17% of extensibility.

What we claim is:

1. A process of spinning artificial threads which comprises squirting a solution of artificial resin comprising a polymeric vinyl compound through a nozzle into a precipitating bath, guiding the threads through the precipitating bath on a length of at least 1 meter and stretching the threads after they have left the spinning bath while in a plastic condition'to at least 2 times the length which the threads would have in case no stretch were applied.

2. A process of spinning artificial threads which comprises squirting a solution of artificial resin comprising a polymeric vinyl compound through a nozzle into a precipitating bath, guiding the threads through the precipitating bath on 7 a length of at least 1 meter and stretching the threads after they have left the spinning bath while in a plastic condition in several stages to at least 2 times the length which the threads would have in case no stretch were applied. 7

' chloride through a length of at least 1 meter while allowing them to shrink and stretching the threads after they have left the spinning bath while in a plastic condition in several stages with successively increasing stretch to at least 2 times the length which the threads would have in case no stretch were applied.

4. A process of spinning artificial threads which comprises squirting a solution of artificial resin comprising a polymeric vinyl compound through a nozzle into a precipitating bath, guiding the threads through the precipitating bath on a length of at least 1 meter, stretching the threads after they have left the spinning bath While in a plastic condition to at least 2 /2 times the length which the threads would have in case no stretch were applied, and allowing the threads to shrink before they are wound on a collecting device.

5. A process of spinning artificial threads which comprises sq ing a solution of an artificial resin comprising a mixed polymeric vinyl compound, containing as a component; a com pound corresponding to the formula: CH2=CCI2; through a nozzle into a precipitating bath, guiding the threads through the precipitating bath on a length of at least 1 meter and stretching the threads after they have left the spinning bath while in a plastic condition to at least 2 times I the length which the threads would have in case no stretch were applied.

6. A process of spinning artificial threads which comprises squirting a solution of an artificial resin comprising a mixed polymeric vinyl compound, containing as a component maleic acid anhydride; through a nozzle into a precipitating bath,- guiding the threads through the precipitating bath on a length of at least 1 meter and stretching the threads after they have left the spinning bath while in a plastic condition to at least 2% times the length which the threads would have in case no stretch were applied.

7. A process of spinning artificial threads which comprises squirting a solution of polyvinyl a nozzle into a precipitating bath guiding the threads through the precipitating bath on a length of at least 1 meter and stretching the threads after they have left the spinning bath while in a plastic condition to at least 2% times the length which the threads would have in case no stretch were applied.

8. A process of spinning artificial threads which comprises squirting a solution of polyvinyl chloride through a nozzle into a precipitating bath. guiding the threads through the precipitating bath on a length of at least 1 meter and stretching the threads after they have left length of at least 1 meter, stretching ing a tensile strength the spinning bath while in a plastic condition in several stages with successively increasing stretch to at least 2 times the length which the threads would have in case no stretch were applied.

9. A process 01' which comprises squirting a solution of afterprecipitating bath of methanol guiding the threads through the precipitating bath on a length of at least 1 meter, stretching the threads after they have left the spinning bath while in a plastic condition to at least 2 times the length which the threads would have in case no stretch were applied.

10. A process of spinning artificial threads which comprises squirting a solution of afterchlorinated polyvinyl-chloride in acetone through a nozzle into a precipitating bath of water, guiding the threads through the precipitating bath on a length of at least 1 meter, stretching the threads after they have left the spinning bath while in a plastic condltionto at least 2% times the length which the threads would have in case no stretch were applied.

11. A process of spinning, artificial threads which comprises acrylic acid ester in acetone through a nozzle into a precipitating bath of water, guiding the threads through the precipitating bath on a the threads after they have left the spinning bath while in a plastic condition to at least 2% times the length which the threads would have were applied.

12. An artificial thread obtained by a process as claimed in claim 1 and consisting substantially of a polymeric vinyl compound and having a the dry state of at least 1.5 grams per denier.

13. An artificial thread obtained by the process in case no stretch squirting a solution of a mixed "polymerization product or polyvinylchloride and as claimed in claim 1 and consisting substantially of polyvinyl-chloride and having a tensile strength in the dry state or at least 1.5 grams per denier.

14. An artificial thread obtained by the process as claimed in claim 1 and consisting substantially of after chlorinated polyvinyl chloride and havin the dry state of at least 1.5 grams per denier.

15. An artificial thread obtained by the process as claimed in claim 1 and consisting substantially of a mixed polymerization product of vinyl chloride and an acrylic acid ester and having a tensile strength in the dry state of at least 1.5 grams per denier.

EMIL HU'BERT. HEINRICH PABST. HERMANN HEOH'I. 

